Preparation method of oxygen vacancy regulated CuO / CeO2 porous catalyst

Abstract

The invention relates to a preparation method of an oxygen vacancy regulated CuO / CeO2 porous catalyst, the CuO / CeO2 porous catalyst is composed of a carrier and an active component, the carrier is carbon and silicon-containing CeO2 with an inverse opal-like structure, the active component is oxygen vacancy-containing CuO or metal-doped CuO, and the content of the active component is 1-30 wt.%. Through regulation and control of the remaining amount of the carbon and silicon components, the pore structure and strength of the carrier, the interaction of the active components and the carrier, and the active oxygen vacancy of the catalyst, the activity and stability of the catalyst are effectively enhanced. The invention provides a novel catalyst for regulating and constructing a porous structure and oxygen vacancies and a method. The structure and composition modulation range of the catalyst is wide; the catalyst can be used for catalyzing CO preferential oxidation reaction under a hydrogen-rich condition, and has an application prospect in other reaction systems catalyzed by a copper oxide base.

Description

Technical Field

[0001] The present invention belongs to the field of energy chemical technology / catalysis, and relates to a method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies, and more specifically to a CuO / CeO2 porous catalyst that can be used for the preferential oxidation reaction of CO under hydrogen-rich conditions. Background Art

[0002] Hydrogen fuel cells, with their high energy conversion efficiency and environmental friendliness, are a crucial area for ensuring energy security and sustainable hydrogen energy development. In particular, they are being used to meet the demands of distributed and portable power generation. Hydrogen fuel cells can be widely used in base stations, homes, commercial buildings, factories, field operations, emergency rescue, and other scenarios, providing stable power with flexible and adjustable power. Within the hydrogen source system of proton exchange membrane hydrogen fuel cells, the CO preferential oxidation reaction (CO-PROX) in a hydrogen-rich atmosphere is a key research topic for improving cell efficiency and lifespan, with highly efficient catalysts being key.

[0003] The high specific surface area of ​​porous structure catalysts not only provides a highly dispersed surface for active components, but also provides a flow channel for reactants. The active components of the catalyst can fully contact the reactants on the surface of the pores, thereby improving the reaction activity. Moreover, the fixed pore structure provided by the porous carrier is conducive to reducing the pressure drop of the reaction bed and improving the reaction efficiency. The development of high-efficiency porous catalysts is a development direction to promote the efficiency of the overall fuel cell system and reduce costs. CeO2-loaded CuO catalyst is one of the effective catalysts for the CO-PROX reaction. Related porous structure catalysts include monolithic catalysts using cordierite, silicon carbide, alumina, ceramics, three-dimensional ordered macroporous catalysts, mesoporous-macroporous catalysts, etc., which reflect the effect of pore structure on the improvement of catalyst reaction performance. The regulation of the carrier pore structure and composition and the structure of the active components is an effective way to develop high-efficiency catalysts. Summary of the Invention

[0004] The present invention provides a method for preparing a CuO / CeO2 porous catalyst with controlled oxygen vacancies. By manipulating the composition and pore structure of the CeO2-based support and the oxygen vacancy formation of the active component CuO, a CuO / CeO2 catalyst with a specific structure is constructed. This catalyst can be used for the preferential oxidation of CO in a hydrogen-rich atmosphere. The preparation method is easily controllable, and the structure and composition are highly adjustable.

[0005] The present invention discloses a method for preparing a CuO / CeO2 porous catalyst with oxygen vacancy regulation. Specifically, the CuO / CeO2 porous catalyst comprises a carrier and an active component, wherein the carrier is CeO2 having a carbon and silicon-containing inverse opal-like structure, and the active component is CuO containing oxygen vacancies or metal-doped CuO, and the content of the active component is 1 to 30 wt.%. The following technical scheme is adopted:

[0006] The silica particles are dispersed in deionized water, centrifuged at 2000-6000 rpm, the supernatant is removed by suction, the lower layer is dried at 60°C, and a mixed aqueous solution of sucrose, cerium salt and ammonia (2 mol / L) is added, the mixture is allowed to stand for half an hour, and freeze-dried. The obtained solid is calcined at 500-650°C for 2-5 hours under a nitrogen atmosphere, and the product is placed in a 1-3 mol / L sodium hydroxide aqueous solution for 4-24 hours to obtain a CeO2 carrier with a carbon and silicon-containing inverse opal structure; the CeO2 carrier is added to a certain amount of a mixed solution of a copper salt aqueous solution and ammonia (2 mol / L), freeze-dried, and the obtained solid is calcined at 500-650°C for 1-4 hours under an air atmosphere to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies.

[0007] The carbon and silicon-containing CeO2 carrier having an inverse opal-like structure has an adjustable silicon content of 5 wt.% to 25 wt.% according to different sodium hydroxide concentrations and treatment time.

[0008] The metal-doped CuO includes at least one metal doping selected from nickel, cobalt, platinum, gold, and ruthenium.

[0009] The cerium salt and copper salt are at least one metal salt selected from nitrate, oxalate, chloride and sulfate.

[0010] The silicon dioxide is spherical particles with a particle size of 200 nm to 10 μm, and the molar ratio of the added amount of silicon dioxide to the cerium salt is 5:1 to 15:1.

[0011] In the mixed aqueous solution of sucrose and cerium salt, the molar percentage of carbon in sucrose to cerium is 10% to 30%.

[0012] After calcining at 500-650° C. for 1-4 hours in the air atmosphere, the carbon content of the obtained CuO / CeO2 porous catalyst is 0wt.%-10wt.%.

[0013] The sodium hydroxide treatment can provide the catalyst with a pore structure similar to an inverse opal skeleton structure; and the calcination process under an air atmosphere provides oxygen vacancy control for the catalyst.

[0014] Preferably, the CuO / CeO2 porous catalyst can be used for the preferential oxidation of CO under hydrogen-rich conditions, with a hydrogen content of 20 vol.% to 70 vol.%.

[0015] The present invention provides a method for preparing a CuO / CeO2 porous catalyst with oxygen vacancy regulation, which has obvious characteristics and is different from the preparation methods of conventional porous catalysts:

[0016] First, the CeO2-like inverse opal pore structure in the CuO / CeO2 porous catalyst of the present invention is unique. It is a porous CeO2 structure containing carbon and silicon, with CeO2 as the main support framework and containing small amounts of silicon oxide and carbon components. The silicon oxide improves the mechanical strength of the support; the amount of silicon oxide is adjustable, directly affecting the support pore structure; and the presence of carbon modulates the structure of the active component and the interaction between the active component and the support, effectively adjusting the catalyst activity and stability.

[0017] Secondly, the regulation of oxygen vacancies in the CuO / CeO2 porous catalyst of the present invention is achieved by means of the in-situ calcination process of CuO on the carbon and silicon-containing CeO2 porous structure support, in which the formation of CuO is accompanied by the oxidation of the carbon component. These two dynamic reaction processes can effectively regulate the generation of oxygen vacancies in the catalyst.

[0018] The method of the present invention can provide a CuO / CeO2 porous catalyst with adjustable oxygen vacancies, which is suitable for CO preferential oxidation reaction under hydrogen-rich conditions and other reaction systems based on copper oxide catalysis. DETAILED DESCRIPTION

[0019] The present invention will be further described below with reference to the following examples, but the present invention is not limited to the following examples. It should be noted that any simple variation, modification, or equivalent replacement that can be made by a person skilled in the art without inventive effort without departing from the core of the present invention falls within the scope of protection of the present invention.

[0020] Example 1:

[0021] 3.00 g of silica particles (average particle size of 200 nm) were dispersed in 20 ml of deionized water and centrifuged at 2000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (1.0269 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The resulting solid was calcined at 500°C for 5 hours under a nitrogen atmosphere. The product was placed in a 3 mol / L sodium hydroxide aqueous solution for 6 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.0304 g of copper nitrate trihydrate and 5 ml of ammonia water (2 mol / L), and freeze-dried. The resulting solid was calcined at 500°C under air atmosphere for 1 hour to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 5 wt.%, a carbon content of 10 wt.%, and a CuO content of 1 wt.%).

[0022] Example 2:

[0023] 9.01 g of silica particles (average particle size of 10 μm) were dispersed in 20 ml of deionized water and centrifuged at 6000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The resulting solid was calcined at 650°C for 2 hours under a nitrogen atmosphere. The product was placed in a 1 mol / L sodium hydroxide aqueous solution for 12 hours to obtain a CeO2 carrier; weigh 1.00 g of the prepared CeO2 carrier, add 0.9111 g of copper nitrate trihydrate and 5 ml of ammonia water (2 mol / L) mixed aqueous solution, freeze-dry, and calcine the resulting solid at 650°C in an air atmosphere for 4 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 25 wt.%, a carbon content of 0 wt.%, and a CuO content of 30 wt.%).

[0024] Example 3:

[0025] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60 ° C. Then, a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 650 ° C for 5 hours under a nitrogen atmosphere. The product was placed in a 1 mol 1 / L sodium hydroxide aqueous solution was treated for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.6074 g of copper nitrate trihydrate and 5 ml of ammonia water (2 mol / L), and freeze-dried. The resulting solid was calcined at 650°C under air atmosphere for 2 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 15 wt.%, a carbon content of 2 wt.%, and a CuO content of 20 wt.%).

[0026] Example 4:

[0027] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60 ° C. Then, a mixed aqueous solution of sucrose (0.6846 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 550 ° C for 5 hours under a nitrogen atmosphere. The product was placed in a 2mo 1 / L sodium hydroxide aqueous solution was treated for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.6074 g of copper nitrate trihydrate and 5 ml of ammonia water (2 mol / L), and freeze-dried. The resulting solid was calcined at 650°C for 2 hours under an air atmosphere to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 10 wt.%, a carbon content of 2 wt.%, and a CuO content of 20 wt.%).

[0028] Example 5:

[0029] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.6846 g), cerium oxalate nine hydrate (7.06 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 550°C for 5 hours under a nitrogen atmosphere. The product was placed in a 2 mol / L / L sodium hydroxide aqueous solution for 24 hours to obtain a CeO2 carrier; weigh 1.00 g of the prepared CeO2 carrier, add 0.2132 g of copper oxalate hemihydrate and 5 ml of ammonia water (2 mol / L) mixed aqueous solution, freeze-dry, and calcine the resulting solid at 650°C under air atmosphere for 2 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 9.5 wt.%, a carbon content of 3 wt.%, and a CuO content of 20 wt.%).

[0030] Example 6:

[0031] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60 ° C. Then, a mixed aqueous solution of sucrose (0.6846 g), cerium chloride heptahydrate (3.72 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 550 ° C for 5 hours under a nitrogen atmosphere and the product was placed in a 2 mo 1 / L sodium hydroxide aqueous solution was treated for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.3215 g of copper chloride dihydrate and 5 ml of ammonia water (2 mol / L), and freeze-dried. The resulting solid was calcined at 550°C under air atmosphere for 2 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 10 wt.%, a carbon content of 3 wt.%, and a CuO content of 20 wt.%).

[0032] Example 7:

[0033] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower layer was dried at 60°C and then added with a mixed aqueous solution of sucrose (0.6846 g), cerium sulfate tetrahydrate (4.05 g) and 10 ml of ammonia water (2 mol / L). The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 550°C for 5 hours under a nitrogen atmosphere. The product was placed in a 3 mol / L L sodium hydroxide aqueous solution for 6 hours to obtain a CeO2 carrier; weigh 1.00 g of the prepared CeO2 carrier, add 0.3139 g of copper sulfate pentahydrate and 5 ml of ammonia water (2 mol / L) mixed aqueous solution, freeze-dry, and calcine the resulting solid at 650°C under air atmosphere for 4 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 5 wt.%, a carbon content of 0.5 wt.%, and a CuO content of 20 wt.%).

[0034] Example 8:

[0035] 6.00 g of silica particles (average particle size of 1 μm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 650°C for 5 hours under a nitrogen atmosphere. The product was placed in a 2 mol / L sodium hydroxide solution. The obtained CeO2 carrier was treated in liquid for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.3037 g of copper nitrate trihydrate, 0.0256 g of cobalt nitrate hexahydrate and 5 ml of ammonia water (2 mol / L), and freeze-dried. The obtained solid was calcined at 650°C in an air atmosphere for 2 hours to obtain a Co-CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 10 wt.%, a carbon content of 2 wt.%, and a CuO content of 10 wt.%).

[0036] Example 9:

[0037] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 650°C for 5 hours under a nitrogen atmosphere. The product was placed in a 2 mol / L sodium hydroxide solution. The obtained CeO2 carrier was treated in the liquid for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.6074 g of copper nitrate trihydrate, 0.0346 g of nickel nitrate hexahydrate and 5 ml of ammonia water (2 mol / L), and the mixture was freeze-dried. The obtained solid was calcined at 650°C in an air atmosphere for 2 hours to obtain a Ni-CuO / CeO2 porous catalyst containing oxygen vacancies (wherein the silicon content was 10 wt.%, the carbon content was 2 wt.%, and the CuO content was 20 wt.%).

[0038] Example 10:

[0039] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The obtained solid was calcined at 650°C for 5 hours under a nitrogen atmosphere. The product was placed in a 2 mol / L sodium hydroxide solution. The obtained CeO2 carrier was treated in a solution for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.6074 g of copper nitrate trihydrate, 0.0225 g of chloroplatinic acid and 5 ml of ammonia water (2 mol / L), and freeze-dried. The obtained solid was calcined at 650°C for 2 hours in an air atmosphere to obtain a Pt-CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 10 wt.%, a carbon content of 2 wt.%, and a CuO content of 20 wt.%).

[0040] Example 11:

[0041] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60° C., and then a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The resulting solid was calcined at 650° C. for 5 hours under a nitrogen atmosphere, and the product was placed in a 2 mol / L sodium hydroxide aqueous solution for 24 hours to obtain a CeO2 carrier. 1.00 g of the prepared CeO2 carrier was weighed, and 0.6074 g of copper nitrate trihydrate, 0.0178 g of chloroauric acid and 5 ml of a solution with a carbon content of 2 wt.%, and a CuO content of 20 wt.% were added.

[0042] Example 12:

[0043] 6.00 g of silica particles (average particle size of 480 nm) were dispersed in 20 ml of deionized water and centrifuged at 4000 rpm. The supernatant was slowly removed by suction. The lower sediment was dried at 60°C, and a mixed aqueous solution of sucrose (0.3423 g), cerium nitrate hexahydrate (4.3422 g) and 10 ml of ammonia water (2 mol / L) was added. The mixture was allowed to stand for half an hour and freeze-dried. The resulting solid was calcined at 650°C for 5 hours under a nitrogen atmosphere. The product was placed in 2 mol / L sodium hydroxide solution. The prepared CeO2 carrier was treated in an aqueous solution for 24 hours to obtain a CeO2 carrier; 1.00 g of the prepared CeO2 carrier was weighed and added to a mixed aqueous solution of 0.6074 g of copper nitrate trihydrate, 0.0189 g of ruthenium chloride and 5 ml of ammonia water (2 mol / L), and freeze-dried. The obtained solid was calcined at 650°C for 2 hours in an air atmosphere to obtain a Ru-CuO / CeO2 porous catalyst containing oxygen vacancies (with a silicon content of 10 wt.%, a carbon content of 2 wt.%, and a CuO content of 20 wt.%).

[0044] Example 13:

[0045] The CuO / CeO2 porous catalysts prepared by the present method were tested for their catalytic activity in the selective oxidation of CO in a hydrogen-rich atmosphere. 0.20g of the catalyst was placed in a fixed-bed reactor with a reaction gas composition of 1 vol.% CO, 2 vol.% O2, 20-70 vol.% H2, and N2 as the balance gas. The total flow rate was 100 mL / min, and the reaction temperature was 100°C or above. All catalysts catalyzed the preferential oxidation of CO.

Claims

1. A method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies, characterized in that: The CuO / CeO2 porous catalyst consists of a carrier and an active component, wherein the carrier is CeO2 with a carbon and silicon-containing inverse opal structure, and the active component is CuO containing oxygen vacancies or metal-doped CuO, and the content of the active component is 1wt.% to 30wt.%. The preparation method is as follows: silica particles are dispersed in deionized water, the solution is centrifuged at 2000 to 6000 rpm, the upper clear liquid is removed by suction, the lower sediment is collected and dried at 60°C for 12 hours, and the dried product is added to a mixture of sucrose, cerium salt and ammonia water (2 mol / L). The aqueous solution is mixed, allowed to stand for half an hour, and freeze-dried. The resulting solid is calcined at 500-650°C in a nitrogen atmosphere for 2-5 hours, and the product is placed in a 1-3 mol / L sodium hydroxide aqueous solution for treatment for 4-24 hours to obtain a CeO2 carrier with a carbon and silicon-containing inverse opal structure; the CeO2 carrier is added to a certain amount of a mixed solution of a copper salt aqueous solution and ammonia water (2 mol / L), and the mixture is freeze-dried. The resulting solid is calcined at 500-650°C in an air atmosphere for 1-4 hours to obtain a CuO / CeO2 porous catalyst containing oxygen vacancies.

2. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The carbon and silicon-containing CeO2 carrier having an inverse opal-like structure has an adjustable silicon content of 5 wt.% to 25 wt.% according to different sodium hydroxide concentrations and treatment time.

3. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The metal-doped CuO includes at least one metal doping selected from nickel, cobalt, platinum, gold, and ruthenium.

4. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The cerium salt is at least one of cerium nitrate, cerium oxalate, cerium chloride and cerium sulfate; the copper salt is at least one of copper nitrate, copper oxalate, copper chloride and copper sulfate.

5. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The silicon dioxide is in the form of spherical particles with a particle size of 200 nm to 10 μm, and the molar ratio of the added amount of silicon dioxide to the cerium salt is 5:1 to 15:

1.

6. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: In the mixed aqueous solution of sucrose and cerium salt, the molar percentage of carbon in the sucrose to cerium is 10% to 30%.

7. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: After calcining at 500-650° C. for 1-4 hours in the air atmosphere, the carbon content of the obtained CuO / CeO 2 porous catalyst is 0 wt.%-10 wt.%.

8. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The sodium hydroxide treatment provides the catalyst with a pore structure similar to an inverse opal skeleton structure; and the calcination process under an air atmosphere provides oxygen vacancy regulation for the catalyst.

9. The method for preparing a CuO / CeO2 porous catalyst regulated by oxygen vacancies according to claim 1, characterized in that: The CuO / CeO2 porous catalyst can be used for CO preferential oxidation reaction under hydrogen-rich conditions, with a hydrogen content of 20 vol.% to 70 vol.%.